Electrochemical oxidative radical trifluoromethylation/semipinacol rearrangement sequences of alkenyl alcohols were developed in this study. This approach is environmentally benign and uses the shelf-stable Langlois reagent as a trifluoromethyl radical precursor and electrons as the oxidizing reagents. The present protocol offers a facile route to prepare β-trifluoromethylated ketone derivatives.